JPH09324098A - Elastomer composition and thermoplastic resin composition modified therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an elastomer which has a low hardness, a high elongation, and excellent tear and tensile characteristics by compounding a vinylarom.- conjugated diene block copolymer and a specific high-rubber graft copolymer.

SOLUTION: This compsn. comprises a vinylarom.-conjugated diene block copolymer (e.g. a PS-polybutadiene block copolymer) and 5wt.% high-rubber graft copolymer comprising 60-95wt.% rubbery polymer substrate layer (e.g. a polybutadiene rubber) which has a glass transition point lower than 0°C and repeating units derived from at least one monoethylenically unsatd. monomer and 40-5wt.% upper hard polymer layer which is grafted at least partly onto the substrate layer, has a glass transition point of 0°C or higher, and has repeating units derived from at least one monomer selected from among an alkyl (meth)acrylate, a vinylarom. compd., and a monoethylenically unsatd. nitrile compd. (e.g. styrene and acrylonitrile).

COPYRIGHT: (C)1997,JPO

Description

Detailed Description of the Invention

FIELD OF THE INVENTION The present invention relates to an elastomer composition and a thermoplastic resin composition modified thereby, and more particularly to an elastomer blend comprising a graft copolymer and a block copolymer and a heat modified thereby. It relates to a plastic resin composition. BACKGROUND OF THE INVENTION In US Pat. No. 3,975,460 to Davidson et al., Acrylonitrile-butadiene-styrene (ABA).
Graft copolymer and selectively hydrogenated styrene-
Polymer blends with conjugated diene block copolymers have been disclosed and are said to exhibit improved processability and high tensile strength.

In Japanese Patent Publication No. 50-006222, 85
A coating composition is disclosed which comprises a mixture of -95 wt% (wt%) ABS copolymer and styrene-butadiene block copolymer having a styrene content of 30-70 wt%. British Patent 1,428,974 discloses blends of suspension polymerized ABS copolymers with styrene-butadiene-styrene block copolymers.

The compositions disclosed above have a relatively low rubber content and these compositions lack elastomeric properties. Therefore, there is now a need for thermoplastic elastomer compositions that exhibit improved properties such as relatively low hardness and high elongation. SUMMARY OF THE INVENTION In a first aspect, the present invention relates to (a) a vinyl aromatic-conjugated diene block copolymer, and (b) at least 5% by weight of a high rubber graft copolymer based on the total weight of the elastomer composition. Comprising coalescing,
60% by weight of a rubbery polymer matrix layer in which the graft copolymer (i) has a glass transition temperature of less than 0 ° C. and contains repeating units derived from one or more mono-ethylenically unsaturated monomers. -95% by weight, and (ii) having a glass transition temperature above 0 ° C. and (C ₁ -C ₁₂ ) alkyl (meth) acrylate monomers, vinyl aromatic monomers and mono-ethylenically unsaturated nitriles. 5% -40% by weight of a rigid polymer upper layer comprising repeating units derived from one or more monomers selected from the group consisting of monomers, and at least one of said rigid polymer upper layers. Parts relating to the elastomeric composition, the parts being grafted to the rubbery polymer matrix layer.

In a second aspect, the present invention provides: (1) 60-98 wt.% Thermoplastic resin having repeating units derived from one or more monomers selected from the group consisting of propylene and 1-methylpentene. %, And (2) (a) a vinyl aromatic-conjugated diene block copolymer, and (b) at least 5% by weight, based on the total weight of the elastomer composition, of a high rubber graft copolymer,
60% by weight of a rubbery polymer matrix layer in which the graft copolymer (i) has a glass transition temperature of less than 0 ° C. and contains repeating units derived from one or more mono-ethylenically unsaturated monomers. -95% by weight, and (ii) having a glass transition temperature above 0 ° C. and (C ₁ -C ₁₂ ) alkyl (meth) acrylate monomers, vinyl aromatic monomers and mono-ethylenically unsaturated nitriles. 5% -40% by weight of a rigid polymer upper layer comprising repeating units derived from one or more monomers selected from the group consisting of monomers, and at least one of said rigid polymer upper layers. A thermoplastic resin composition comprising 2-40% by weight of an elastomeric composition, parts of which are grafted to the rubbery polymer matrix layer.

The elastomeric compositions of the present invention exhibit relatively low hardness and relatively high elongation as well as improved tear and tensile properties, and the thermoplastic resin compositions of the present invention have improved impact strength and improved. Shows abrasion resistance. Detailed Description of the Invention I: Elastomer Composition In a preferred embodiment, the elastomer composition of the present invention is 20-80 wt%, more preferably 30-70.
wt% and more preferably 40-70 wt% vinyl aromatic-conjugated diene block copolymer and 20-80.
wt%, more preferably 30-70 wt% and even more preferably 30-60 wt% graft copolymer.

A: Vinyl aromatic-conjugated diene block copolymer
In the polymer preferred embodiment, the vinyl aromatic - conjugated diene block copolymer is represented by Formula 1 or 2 shown below. AB (1) or ABA (2) where A is a number average molecular weight of 1,000-10 consisting of repeating units derived from one or more vinyl aromatic monomers.
B is a block having a number average molecular weight of 10,000-500,000 consisting of repeating units derived from conjugated diene monomers.

In an even more preferred embodiment,
The A block of the block copolymer is 2,000-50,0
00 or more preferably 10,000-40,0
Independently of this, the B block of the block copolymer has a number average molecular weight of 00,
000 or more preferably 50,000-20
It has a number average molecular weight of 000.

Suitable vinyl aromatic monomers include, for example, styrene and substituted styrenes having one or more alkyl, alkoxy, hydroxyl or halo substituents attached to the aromatic ring such as α-methylstyrene, p-methyl. Styrene, vinyltoluene, vinylxylene, tolmethylstyrene, butylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, p-hydroxystyrene,
Included are methoxystyrene, vinyl substituted fused aromatic ring structures such as vinylnaphthalene, vinylanthracene, as well as mixtures of these vinylaromatic monomers. In a preferred embodiment, the vinyl aromatic monomer of the vinyl aromatic-conjugated diene block copolymer is styrene or α-methylstyrene.

Suitable conjugated diene monomers include, for example, 1,
3-butadiene, isoprene, 1,3-heptadiene,
Methyl-1,3-pentadiene, 2,3-dimethylbutadiene, 2-ethyl-1,3-pentadiene, 1,3-
Hexadiene, 2,4-hexadiene, dichlorobutadiene, bromobutadiene and dibromobutadiene and mixtures of these conjugated diene monomers are included. In a preferred embodiment, the conjugated diene monomer of the vinyl aromatic-conjugated diene block copolymer is 1,3-butadiene.

The B block of the block copolymer may contain residual unsaturated sites or may be almost completely saturated by hydrogenation after polymerization. In a preferred embodiment, the vinyl aromatic-conjugated diene block copolymer contains a low amount of residual unsaturation, for example less than 20%, more preferably less than 10%, even more preferably less than 5%.

Suitable vinyl aromatic-conjugated diene block copolymers such as polystyrene-polybutadiene block copolymers, polystyrene-polybutadiene-polystyrene block copolymers, polystyrene-isoprene-polystyrene block copolymers, polystyrene-poly (ethylene- Butylene) -polystyrene block copolymers (i.e. hydrogenated polystyrene-polybutadiene-polystyrene block copolymers) and methods for making such vinyl aromatic-conjugated diene block copolymers are well known in the art, and Such copolymers are for example Shell
KRATON® D series rubbers and KRATON® G series hydrogenated rubbers are commercially available from Chemical Company.

In a preferred embodiment, the vinyl aromatic-conjugated diene block copolymer is a polystyrene-polybutadiene block copolymer, polystyrene-polybutadiene-polystyrene block copolymer or polystyrene-poly (ethylene-butylene) -polystyrene block. It is a copolymer. B: Graft Copolymer In a preferred embodiment, the rubbery polymer matrix layer has a glass transition temperature "Tg" of less than -20 ° C. In the present specification, the Tg of a polymer is the Tg value measured by differential scanning calorimetry (at a heating rate of 20 ° C./min, the Tg value is measured at the inflection point).

In a preferred embodiment, the graft
The copolymer is 65 wt% -90 wt%, more preferably 6
5 wt% -80 wt% rubbery polymer matrix layer and 10
wt% -35 wt%, more preferably 20 wt% -35
Includes wt% hard polymer top layer.i: rubbery polymer substrate layer As used herein, the term "mono-ethylenic
"Saturated" has only one ethylenically unsaturated site in the molecule
Means that. In a preferred embodiment, rubber
Polymeric polymer substrate layer is conjugated diene monomer, non-conjugated diene monomer
Body, (C₁-C ₁₂) Alkyl acrylate monomer and
One or more mono-ethyl compounds selected from vinyl aromatic monomers
It contains repeating units derived from lenically unsaturated monomers.

Suitable vinyl aromatic monomers and conjugated die
The monomer is a vinyl aromatic-conjugated diene block of the present invention.
It was already disclosed in the description of the copolymer. Appropriate
Non-conjugated diene monomers include, for example, ethylidene norbornene.
, Dicyclopentadiene, hexadiene or phenyl
Includes Renorbornene. Used herein
Term "(C_Two-C₈) "Olefin monomer" has 2 molecules
-8 carbon atoms and unique ethylenic in the molecule
It means a compound containing an unsaturated site. Appropriate (C _Two-C
₈) Examples of olefin monomers include ethylene and propene.
And 1-butene, 1-pentene and heptene.
As used herein, the term "(C₁-C₁₂) Al
"Kill" refers to a straight chain containing from 1 to 12 carbon atoms in the group.
Or branched alkyl substituents and for example methyl,
Ethyl, n-butyl, sec-butyl, t-butyl, n-
Propyl, iso-propyl, pentyl, hexyl, hep
Chill, octyl, nonyl, decyl, undecyl and do
Including decyl. Appropriate (C₁-C₁₂) Alkyl acryl
For example, ethyl acrylate, butyl acrylate
, Iso-pentyl acrylate, n-hexyl acrylate
Rate, including 2-ethylhexyl acrylate.
As used herein, the term "mono-ethylenic
"Saturated nitrile monomer" is the only nitrile group and only one in the molecule
Means an acrylic compound containing an ethylenically unsaturated moiety of
And, for example, acrylonitrile, methacrylonitrile
Including.

In a preferred embodiment, the rubbery polymer matrix layer comprises 30-90 wt% of repeating units derived from one or more conjugated diene monomers and vinyl aromatic monomers and mono-ethylenically unsaturated nitriles. Repeating units derived from one or more monomers selected from monomers 10-
Contains 70 wt%. The rubbery polymer matrix layer is optionally derived from poly-ethylenically unsaturated "crosslinkable" monomers such as butylene diacrylate, divinylbenzene, butanediol dimethacrylate, trimethylolpropane tri (meth) acrylate. Repeating units may be included in small amounts, eg up to 5 wt%. As used herein, the term “poly-ethylenically unsaturated” means having two or more sites of ethylenic unsaturation in the molecule.

The rubbery polymer matrix layer is, for example, of allyl methacrylate, diallyl maleate, triallyl cyanurate, especially when the rubbery matrix layer has repeating units derived from alkyl (meth) acrylate monomers. , Which induces the substrate layer or the upper layer, respectively.
A small amount of repeating units derived from a poly-ethylenically unsaturated "graft-bonding" monomer, such as 3 wt%, where the reactivity of the ethylenically unsaturated site is substantially different from the ethylenically unsaturated monomer. Can be included.

In a first highly preferred embodiment, the substrate layer is a polybutadiene rubber which contains repeating units derived from one or more conjugated diene monomers, eg is a substantially homopolymer. In a second highly preferred embodiment, the substrate layer is one or more copolymerizable one or more selected from conjugated diene monomers and vinyl aromatic monomers and mono-ethylenically unsaturated nitrile monomers. It contains repeating units derived from various copolymerizable monomers, such as styrene-butadiene copolymer, acrylonitrile-butadiene copolymer and styrene-butadiene-acrylonitrile copolymer. In a highly preferred embodiment, the matrix layer comprises 60-95 wt% repeat units derived from one or more conjugated diene monomers.

In a third highly preferred embodiment
Has one or more substrate layers (C₁-C ₁₂) Alkyl acrylate
It contains repeating units derived from rate monomers. Greater
In a preferred embodiment for the rubbery polymer matrix layer
Is more than one (C₁-C₁₂) Alkyl acrylate unit
More preferably body, ethyl acrylate, butyl acrylate
And one selected from n-hexyl acrylate.
40-95w repeating units derived from more than one monomer
Includes t%.

In a fourth highly preferred embodiment, the substrate layer comprises a first repeating unit derived from one or more olefin monomers and a second repeating unit derived from one or more non-conjugated diene monomers. It contains repeating units, for example ethylene / propylene copolymers, ethylene / propylene / non-conjugated diene monomer terpolymers. Suitable rubbery polymer matrix layers are prepared by known methods such as emulsion polymerization and bulk polymerization.

In a preferred embodiment, the rubbery polymeric substrate layer is in the presence of a free radical initiator such as an organic peroxide or persulfate initiator or redox initiator system, and optionally a chain transfer agent. For example, it is produced by aqueous emulsion polymerization in the presence of alkyl mercaptan. In a preferred embodiment, the emulsion polymerized rubbery polymer matrix layer is in the form of particles and has a 50-
1000 nanometers (nm), more preferably 50-
It has a weight average particle size of 600 nm. The rubbery polymer matrix layer may exhibit a monomodal particle size distribution or a multimodal, eg bimodal particle size distribution. An example of a bimodal particle size distribution is, for example, 50-80 wt% particles having a size in the range 80-180 nm, and for example 2
20 particles having a particle size in the range of 50-1000 nm
-50 wt% is included.

In another preferred embodiment in which the rubbery polymer matrix layer is produced by bulk polymerization, the rubbery polymer matrix layer is in the form of particles and has a thickness of 50-1000 n.
m, more preferably 50-500 nm weight average particle size. ii: Hard Polymer Top Layer The hard polymer top layer is from the group consisting of (C ₁ -C ₁₂ ) alkyl (meth) acrylate monomers, vinyl aromatic monomers and mono-ethylenically unsaturated nitrile monomers. It contains repeating units derived from the monomer of choice. Suitable vinyl aromatic monomers and mono-ethylenically unsaturated nitrile monomers have already been mentioned above. As used herein, the term “(C ₁ -C ₁₂ ) alkyl (meth) acrylate monomer” refers collectively to acrylate and methacrylate monomers. Suitable alkyl (meth) acrylate monomers include the acrylate monomers disclosed above as well as their methacrylate analogs such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, iso-propyl methacrylate, butyl methacrylate, hexyl methacrylate, decyl methacrylate. Is included.

In a highly preferred embodiment, the top layer comprises repeating units derived from one or more monomers selected from styrene, α-methylstyrene and acrylonitrile. In a more preferred embodiment,
The upper layer is a repeating unit 60-90w derived from styrene.
Repeating unit 1 derived from t% and acrylonitrile
Including 0-40 wt%.

In another highly preferred embodiment, the top layer comprises repeating units derived from one or more (C ₁ -C ₁₂ ) alkyl (meth) acrylate monomers, optionally further vinyl aromatic. It may include repeating units derived from one or more monomers selected from monomers and mono-ethylenically unsaturated nitrile monomers. In a particularly preferred embodiment, the hard polymer top layer comprises one or more (C ₁ -C ₁₂ ) alkyl (meth) acrylate monomers, more preferably methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate and butyl methacrylate. 50 w of repeating units derived from one or more selected monomers
Contains t% or more.

As long as the respective Tg limits are met, the rubbery substrate layer and the hard top layer are each independently a repeating unit derived from one or more other copolymerizable ethylenically unsaturated monomers. May be included in small amounts, for example up to 15 wt% of the total weight of each of the substrate layer or the top layer. Suitable Monomers Copolymerizable with the Monomers Above
Examples of ethylenically unsaturated monomers include mono-ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid; hydroxy (C ₁ -C ₁₂ ) alkyl (meth)
Acrylate monomers such as hydroxyethyl methacrylate; (C ₄ -C ₁₂ ) cycloalkyl (meth) acrylate monomers such as cyclohexyl methacrylate; (meth) acrylamide monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate and propionic acid. Contains vinyl. As used herein, the term “(C ₄ -C ₁₂ ) cycloalkyl” includes 4
A cyclic alkyl substituent having -12 carbon atoms is meant, and the term "(meth) acrylamide" refers collectively to acrylamide and methacrylamide.

The hard polymer top layer is optionally a small amount of repeating units derived from one or more poly-ethylenically unsaturated crosslinkable monomers, for example up to 3 wt%, more preferably 1.5.
It can be included up to wt%. Suitable crosslinkable monomers have already been mentioned above. The graft copolymer may be prepared according to known methods under conditions such that at least a portion of the hard polymer top layer is chemically grafted to the rubber polymer substrate layer via covalent bonds. Prepared by polymerizing one or more monomers selected to provide a hard polymer top layer having the desired Tg in the presence of the particles. In a preferred embodiment, the upper layer monomers are polymerized by an aqueous emulsion or aqueous suspension polymerization reaction in the presence of substrate layer particles and a polymerization initiator system such as heat or a redox initiator system. Accordingly, a part of the chain of the polymerization process of the upper layer monomer is chemically bonded or graphed to the substrate layer through the reaction with the unsaturated site in the substrate layer. Unsaturation sites in the substrate layer are provided, for example, by residual unsaturation sites in the repeating unit derived from the conjugated diene or by residual unsaturation sites in the repeating unit derived from the graft-linking monomer. In a preferred embodiment, at least 30 wt% of the hard polymer top layer, preferably 6
Greater than 0 wt% is chemically grafted to the rubbery polymer matrix layer, and less than 70 wt%, preferably less than 40 wt% of the hard polymer top layer remains ungrafted.

The top layer can be polymerized from a suitable monomer or mixture of suitable monomers in a single step, or the phases of two or more hard polymer top layers of different composition can be polymerized separately. Can be formed by, for example, a methyl methacrylate phase and a separately polymerized styrene phase. In a first preferred embodiment, the substrate layer comprises repeating units derived from one or more conjugated diene monomers and optionally further vinyl aromatic monomers and mono-ethylenically unsaturated nitrile monomers. May include repeating units derived from one or more monomers selected from, and the upper layer comprises one or more monomers selected from vinyl aromatic monomers and mono-ethylenically unsaturated nitrile monomers. Containing repeating units derived from monomers such as acrylonitrile-
An example is a butadiene-styrene (ABS) high rubber graft copolymer. Suitable ABS type high rubber graft copolymers are commercially available from GE Specialty Chemicals, Inc. as eg B
LENDEX® 336 and BLENDEX
It is commercially available as (registered trademark) 338 modifier.

In a second preferred embodiment, the substrate layer comprises repeating units derived from one or more (C ₁ -C ₁₂ ) alkyl acrylate monomers and the top layer comprises vinyl aromatic monomers and It contains repeating units derived from one or more monomers selected from mono-ethylenically unsaturated nitrile monomers, such as styrene-acrylate (S
A) high rubber graft copolymer and acrylonitrile-styrene-acrylate (ASA) high rubber graft copolymer are exemplified. Suitable ASA type graft copolymers are commercially available from GE Specialty Chemicals, Inc., such as BLE.
It is commercially available as NDEX® 980 modifier.

In a third preferred embodiment, the substrate layer comprises repeating units derived from one or more conjugated diene monomers and optionally further comprises (C ₁ -C ₁₂ ) alkyl (meth) acrylate monomers. Monomers, repeating units derived from one or more monomers selected from vinyl aromatic monomers and mono-ethylenically unsaturated nitrile monomers, and the top layer comprises one or more (C ₁ -C ₁₂₎ alkyl (meth) include repeating units derived from acrylate monomers and optionally further vinyl aromatic monomers and mono - ethylenically least one single selected from unsaturated nitrile monomer It may contain repeating units derived from a polymer such as methylmethacrylate-acrylonitrile-butadiene-styrene (MABS) high rubber graft copolymer and methacryl. Rate-butadiene-styrene (M
BS) high rubber graft copolymer is exemplified. Suitable M
BS type graft copolymer is Rohm and Hass Compan
PARALOID® B commercially available from y
TA-733 and BTA-753 and Kaneka Texas
Kane Ace B-56, commercially available from

In a fourth preferred embodiment, the substrate layer comprises repeating units derived from one or more olefinic monomers and optionally further repeating units derived from one or more non-conjugated diene monomers. Units and the top layer comprises repeating units derived from one or more monomers selected from vinyl aromatic monomers and mono-ethylenically unsaturated nitrile monomers, such as acrylonitrile-
An example is an ethylene-propylene-styrene (AES) high rubber graft copolymer.

In a fifth preferred embodiment, the substrate layer comprises repeat units derived from one or more (C ₁ -C ₁₂ ) alkyl acrylate monomers and the top layer comprises one or more (C ₁ -C _1-). include C ₁₂₎ alkyl (meth) repeating units derived from acrylate monomers, for example acrylic "core - shell" graft copolymers. Suitable acrylic type graft copolymers are Rohm and H
PARALOID® KM334 and KM355 modifiers commercially available from ass Company.

Graft copolymers based on a substantially fully saturated rubbery polymer matrix layer, such as, for example, ASA type, SA type, acrylic type and AES type graft copolymers, include, for example, butadiene rubber. Compared to graft copolymers based on rubbery polymer matrix layers containing a high degree of residual unsaturation such as the base graft copolymers, they have better weather resistance, exposure to sunlight and cycling of temperature and humidity levels. It is highly resistant to degradation by exposure to changes in water and is therefore preferred for applications where it is expected to be associated with exposure to the outdoor environment.

In a highly preferred embodiment of the elastomeric composition, the vinyl aromatic-conjugated diene block copolymer is substantially fully saturated by, for example, hydrogenating residual unsaturation after polymerization of the copolymer. And the rubbery substrate layer of the graft copolymer is derived from an alkyl acrylate, preferably butyl acrylate, and the upper layer is derived from vinyl aromatic monomers, preferably styrene and nitrile monomers, preferably acrylonitrile.

II. Thermoplastic Resin Composition In a preferred embodiment, the thermoplastic resin composition of the present invention comprises 60-90 wt% thermoplastic resin and 10-40 wt% elastomer composition. Suitable thermoplastics and methods of making thermoplastics are known in the art, and such resins include homopolymers of polypropylene and poly (1-methylpentene) and propylene or 1-methylpentene and others. Monomers, preferably copolymers with other olefin monomers such as poly (propylene-ethylene) and poly (propylene-butene) are included. In a highly preferred embodiment, the thermoplastic resin is polypropylene homopolymer.

The elastomeric and thermoplastic resin compositions of the present invention are optionally effective to further increase the heat distortion temperature of the composition, eg, polyphenylene ether in an amount up to 40 wt% of the total weight of each composition. It may include a resin. Suitable polyphenylene ether resins are disclosed by reference in U.S. Pat. No. 4,404,125 and U.S. Pat. No. 4,771,096. In a preferred embodiment, the polyphenylene ether resin is 2,6-dimethylphenol and 2,6-dimethylphenol.
It contains repeating units derived from one or more of 3,6-trimethylphenol.

The respective compositions of the elastomers and thermoplastics of the present invention may include other additives known in the art such as reinforcing fillers, pigments, colorants, flame retardants, antistatic agents, plasticizers, oils. , Lubricants, antioxidants, UV stabilizers, heat stabilizers and costabilizers. The respective compositions of elastomers and thermoplastics according to the invention are produced, for example, by melt-mixing the components, for example in a uniaxial or biaxial compounder equipped with a two-roll mill, a Banbury mixer or kneading elements. The materials described in this invention can be formed into useful articles by various means such as injection, extrusion, spin and blow molding or thermoforming.

The elastomeric compositions of the present invention are particularly well suited for applications requiring low hardness and high elongation in articles such as shoe soles, gaskets. The thermoplastic resin composition of the present invention is particularly well suited for applications requiring impact strength in articles such as thermoformed automotive interior panels and blow molded containers. The vinyl aromatic-conjugated diene block copolymer is substantially fully saturated and the rubbery polymeric substrate layer of the graft copolymer is an acrylate rubber, ethylene-propylene rubber or ethylene-propylene-non-conjugated diene rubber, i.e. Graft copolymer is AS
A type, SA type, acrylic type and AES
In the case of the highly preferred embodiment of the elastomer composition of the present invention, which is a graft copolymer of the type described, as well as the embodiment of the thermoplastic resin composition of the present invention including such an elastomer composition, The composition exhibits excellent weatherability and is therefore particularly well suited for use in articles intended for outdoor use.

[0037] Example vinylaromatic - conjugated diene block copolymer Examples 1-9 and Comparative Examples by mixing 5 minutes melt at 171 ° C. in a two roll mill for laboratory and graft copolymer A
Blends of ABS graft copolymer / SBS block copolymer and ABS graft copolymer / SB block copolymer were prepared. The test sample was pressed at 174 ° C.

Samples of the compositions of Examples 1-9 and Comparative Example A were subjected to the following tests. Tensile Strength, Tensile Elongation and Tensile Modulus by ASTM D-412; Tear Resistance by ASTM D-624 using Die C; AST
Hardness according to MD-2240 (Shore A and Shore D). In Table 1 below, the comparative compositions of Examples 1-9 and Comparative Example A, respectively, are expressed in parts by weight (pbw), tensile strength and tensile yield strength are expressed in pounds per square inch (PSI), and tensile elongation is Expressed in percent (%), tear strength and tear yield strength are reported in pounds per linear inch (lbs).
/ In) and the capillary viscosities measured at several different shear rates, expressed in poise.

The thermoplastic resin compositions of Examples 10-21 and Comparative Example B were combined by combining a vinyl aromatic-conjugated diene block copolymer and a graft copolymer by the two roll mill method as described above. Then the blend thus obtained is subjected to 250 using a two-roll mill.
It was prepared by melt mixing with a thermoplastic polymer for 5 minutes at 0 ° C. This thermoplastic resin composition was subjected to an impact test (1/8 inch Izod). In Table 2 below, the comparative compositions and foot pounds / of the compositions of Examples 10-21 and Comparative Example B are shown.
The results of the impact test in inches (ft-lb / in) are shown.

The ASA graft copolymer / hydrogenated SBS block copolymer blends of Examples 22-24 and Comparative Examples C, D and E were prepared by the two roll mill method described above. The tensile performance of this composition is A
Tested according to STM D-412 at a crosshead speed of 20 inches / minute. In Table 3 below, the comparative composition of the compositions of Examples 22-24 and Comparative Examples C, D and E is expressed in pbw and the test results, ie maximum stress in pounds per square inch (PSI), yield strain The breaking strain was expressed in%, Young's modulus was expressed in PSI, and stress at 100% strain was expressed in PSI.

The MBS graft copolymer / hydrogenated SBS block copolymer blends of Examples 25-26 were prepared by the method using the two roll mill described above.
Samples of the compositions of Examples 25-26 were subjected to the following tests. Tensile Strength, Tensile Elongation and Tensile Modulus according to ASTM D-412; Tear resistance using Die C according to ASTM D-624; Hardness according to ASTM D-2240 (Shore A and Shore D).

In Table 4 below, the comparative compositions of the compositions of Examples 25-26 are expressed in pbw and the test results, tensile strength in pounds per square inch (PSI), tensile elongation in percent (%). ) And the tear strength and tear yield strength are expressed in pounds / linear inch (lbs / in). Table 1 Example A 1 2 3 4 5 6 7 8 9 SBS1 100 70 50 30 70 50 ---- ---- SBS2 ---- ---- ---- 70 50 30 70 ABS1 --30 50 70 ---- 30 50 70 --ABS2 ---- ---- 30 50 ---- --30 Hardness Shore A 70 77 80 85 74 76 68 75 83 65 Shore D 24 29 33.5 38 26 29 21 25 32 19.5 Tensile strength PSI 1720 2646 2032 1422 1944 1857 475 693 979 564 Elongation% 1598 1197 677 325 1325 934 681 409 264 1276 Yield strength PSI 257 376 447 586 308 337 217 317 501 501 182 Elongation% 23 18 14 9 25 20 14 12 9 14 Tear strength lbs / in 224 337 391 384 301 333 159 205 284 145 Break strain% 491 265 114 717 360 437 146 94 552 Yield strength lbs / in 449 674 782 769 602 665 171 163 239 184 Capillary viscosity poise 100 / sec 48747 43475 44490 46552 47598 50682 18252 24049 35487 17846 500 / sec 11984 10759 10267 11823 11535 12323 6506 7819 10343 6450 1000 / sec 6396 5804 5843 6486 6152 6598 4079 4766 6093 4042 `` SBS1 '' is Shell Chemical Trade name from Company Kr
Polystyrene commercially available as aton1101
It is a polybutadiene-polystyrene triblock copolymer.

"SBS2" is a polystyrene-polybutadiene diblock copolymer commercially available from Shell Chemical Company under the trade name Kraton 1118. "ABS1" is an acrylonitrile-butadiene-styrene graft copolymer having 70% by weight of the polybutadiene rubber of polybutadiene rubber sold under the tradename Blendex 338 from the General Electlic company.

"ABS2" is a General Electlic company
Polybutadiene-styrene rubber, commercially available under the tradename Blendex 336 from
It is an acrylonitrile-butadiene-styrene graft copolymer having 5% by weight. Table 2 Example B 10 11 12 13 14 15 16 17 18 19 20 21 PP 100 81 81 76 76 76 71 75 70 75 70 71 66 ABS1 --15 --20 ---- ---- ---- ---- --ABS2 ---- 15 --20 15 20 25 30 ---- 25 30 SBS1 --4 4 4 4 ---- ---- 25 30 4 4 SBS2 ----- ----- 4 4 --------1 / 8in izotto (ft-lbs 0.93 0.91 1.42 1.01 2.28 1.49 1.37 0.95 0.96 5.88 10.4 2.84 3.2 / in) "PP" is from Montell It is a polypropylene resin commercially available under the trade name Profax6501.

Compositions B and 10-15 were hindered phenolic compounds (0.05 wt% -Irganox1).
010 antioxidant), phosphite (0.1 wt% -Ul)
transox 626), calcium stearate (0.
1 wt%) and EBS wax (0.1 Wt%). Table 3 Example D E 22 23 24 C BC3 70 50 70 50 30 30 100 ASA3 30 50 ---- ---- ASA4 ---- 30 50 70 --EBS wax 0.3 0.3 0.3 0.3 0.3 0.3 Hardness: Shore A 88 91 72 67 62 76 Hardness: Shore D 42 54 27 24 22 28 Yield strain% 11 8 27 17 21 732 Maximum stress PSI 1551 1822 2877 1253 1088 4456 Fracture strain% 302 76 1107 687 702 1173 Young's modulus PSI 10817 27924 3388 2628 2181 3155 100% strain stress PSI 1146 --352 316 282 404 "BC3" is trade name KRA from Shell Chemical Company
Styrene / ethylene-butylene / styrene block copolymer (also called hydrogenated styrene-butadiene-styrene block copolymer) commercially available as TON G1650.

"ASA3" is an acrylonitrile-styrene-butyl acrylate graft copolymer containing 35% by weight rubber. "ASA4" is an acrylonitrile-styrene-butyl acrylate graft copolymer containing 75% by weight rubber. Table 4 Example 25 26 SBS1 50 50 MBS1 50 --MBS2 --50 Hardness: Shore D 26 24 Hardness: Shore A 78 80 Tear strength lbs / in 258 246.9 Yield strength PSI 515.9 493.7 Tensile elongation% 33 797 Tensile strength PSI 1080 1060 "MBS1" is trade name Paraloid BTA753
Is a methyl methacrylate-butadiene-styrene graft copolymer containing at least 70% by weight of rubber.

"MBS2" is a trademark name Paraloid
At least 65 rubbers commercially available as BTA733
It is a methylmethacrylate-butadiene-styrene graft copolymer containing by weight.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location C08L 53:02 51:04) (72) Inventor Roman W. Wypert West Virginia, USA, Parkersburg, South Lake Drive, number 40

Claims (10)

[Claims] 1. A composition comprising (a) a vinyl aromatic-conjugated diene block copolymer, and (b) at least 5% by weight, based on the total weight of the elastomer composition, of a high rubber graft copolymer,
60% by weight of a rubbery polymer matrix layer in which the graft copolymer (i) has a glass transition temperature of less than 0 ° C. and contains repeating units derived from one or more mono-ethylenically unsaturated monomers. -95% by weight, and (ii) having a glass transition temperature above 0 ° C. and from the group consisting of alkyl (meth) acrylate monomers, vinyl aromatic monomers and mono-ethylenically unsaturated nitrile monomers. 5% -40% by weight of a rigid polymer upper layer comprising repeating units derived from one or more selected monomers, at least a portion of said rigid polymer upper layer comprising said rubbery polymer An elastomeric composition grafted to a matrix layer. 2. The block copolymer according to claim 1, which is a polystyrene-polybutadiene block copolymer, a polystyrene-polybutadiene-polystyrene block copolymer or a polystyrene-poly (ethylene-butylene) -polystyrene block copolymer. Composition. 3. The substrate layer comprises repeating units derived from one or more conjugated diene monomers, and the upper layer is selected from vinyl aromatic monomers and mono-ethylenically unsaturated nitrile monomers. The composition of claim 1 comprising repeat units derived from one or more monomers. 4. The substrate layer comprises repeating units derived from one or more (C ₁ -C ₁₂ ) alkyl acrylate monomers, and the top layer is a vinyl aromatic monomer and a mono-ethylenically unsaturated nitrile. The composition of claim 1, comprising repeating units derived from one or more monomers selected from monomers. 5. The substrate layer comprises repeating units derived from one or more conjugated diene monomers, and the upper layer is derived from one or more (C ₁ -C ₁₂ ) alkyl (meth) acrylate monomers. The composition of claim 1 comprising a repeating unit of: 6. A substrate layer comprising repeating units derived from one or more olefin monomers, and an upper layer selected from vinyl aromatic monomers and mono-ethylenically unsaturated nitrile monomers. The composition according to claim 1, comprising repeating units derived from the above monomers. 7. The substrate layer comprises repeating units derived from one or more (C ₁ -C ₁₂ ) alkyl acrylate monomers, and the top layer is one or more (C ₁ -C ₁₂ ) alkyl (meth). The composition of claim 1 comprising repeat units derived from an acrylate monomer. 8. The composition according to claim 1, comprising 20-80% by weight of the block copolymer and 20-80% by weight of the graft copolymer. 9. A graft copolymer having a substrate layer of 65-90.
%, And 10-35% by weight of the top layer.
A composition as described. 10. A thermoplastic resin 60-98% by weight having a repeating unit derived from at least one monomer selected from the group consisting of propylene and 1-methylpentene, and (2) (a). ) A vinyl aromatic-conjugated diene block copolymer, and (b) at least 5% by weight of a high rubber graft copolymer, based on the total weight of the elastomeric composition,
60% by weight of a rubbery polymer matrix layer in which the graft copolymer (i) has a glass transition temperature of less than 0 ° C. and contains repeating units derived from one or more mono-ethylenically unsaturated monomers. -95% by weight, and (ii) having a glass transition temperature above 0 ° C. and from the group consisting of alkyl (meth) acrylate monomers, vinyl aromatic monomers and mono-ethylenically unsaturated nitrile monomers. 5% -40% by weight of a rigid polymer upper layer comprising repeating units derived from one or more selected monomers, at least a portion of said rigid polymer upper layer comprising said rubbery polymer Elastomer composition 2-4 grafted on substrate layer
A thermoplastic resin composition comprising 0% by weight.